Fatty acid chromium complex salts and compositions thereof

ABSTRACT

THIS INVENTION IS A METHOD FOR PRODUCING A WATER REPELLING COMPOSITION COMPRISING REACTING A FATTY ACID METALLIC SALT WITH BASIC CHROMIC SULPHATE AND THE COMPOSITION ITSELF.

United States Patent 3,558,676 FATTY ACID CHROMIUM COMPLEX SALTS ANDCOMPOSITIONS THEREOF Edward E. Doherty, P.O. Box 2332,

Buford, Ga. 30518 N0 Drawing. Filed Apr. 19, 1967, Ser. No. 631,851 Int.Cl. C07c 143/90; C11d 1/28 US. Cl. 260-400 13 Claims ABSTRACT OF THEDISCLOSURE This invention is a method for producing a water repellingcomposition comprising reacting a fatty acid metallic salt with basicchromic sulphate and the composition itself.

BACKGROUND This invention relates to compounds for use in treatingvarious materials to render them water resistant or repellent. Moreparticularly, this invention relates to a fatty acid chromium complexsalt for use in impregnating and coating various materials to renderthem water resistant or repellent and to the method for producing suchcompounds.

The art of rendering materials Water resistant or repellent byimpregnation and coating with hydrophobic compounds is old and wellknown. However, many of the prior art compounds and compositions arequite expensive and are not of a permanent nature. For example, in manyinstances when a material has been treated with a prior art hydrophobiccompound the compound will the easily removed after several washings ordry cleanings. This is particularly prevalent with fabrics andnecessitates their being periodically retreated. Moreover, certain ofthese hydrophobic compounds will impart water resistance or repellencyonly to certain materials and thus have but limited use. In addition,some of these compounds produce a resistance to dyeing thereby creatingcertain disadvantages when used to treat textile materials.

BRIEF DESCRIPTION OF THE INVENTION In accordance with this invention,there is provided a compound comprising a fatty acid chromium complexsalt for use in treating various materials to render them permanentlyWater repellent and resistant. A method of producing this compound isalso provided and generally comprises reacting a metallic salt of afatty acid with basic chromic sulphate.

As previously mentioned, the primary use of this com pound is intreating porous materials to render them Water resistant and repellent.The treatment may include the usual impregnation and coating techniquespresently practiced in the art. The results of the treatment produce aresistance to water which is of a substantially permanent nature. Theapparent reason for this is that the compound, upon drying, becomeshighly insoluble in water as well as insoluble in conventionalhydrocarbon solvents which are used in the dry cleaning industry andaround the home.

It is, therefore, a primary object of this invention to provide a newcompound for use in treating various materials to render them waterresistant and repellent.

Another object of this invention is to provide a method for producing anew compound for use in treating various materials to render them waterresistant and repellent.

A further object of this invention is to provide a fatty acid chromiumcomplex salt for use in treating porous materials to render them waterresistant and repellent.

Another object of this invention is to provide a method of making afatty acid chromium complex salt.

Another object of this invention is to provide a fatty acid chromicsulphate complex for use in imparting substantially permanent waterresistance to porous materials.

Other objects and features of this invention will become apparent fromthe following detailed description and the accompanying examples.

The fatty acid chromium complex salts of this invention are coordinationcompounds of the Werner type. According to the Werner Theory, atoms mayexert auxiliary or secondary valences as well as the principal orprimary valences occurring in simple compounds. Even though the primaryvalence-combining capacity of such atoms may become exhausted, the atomsmay still combine with other atoms, radicals, or molecules by means ofthe secondary valences. The central atom which exerts both primary andsecondary valences together with its coordinated group or groups isreferred to as a complex and functions as a unit.

With particular reference to chromium, it has been found that the totalnumber of groups which may be held within the complex by the primary andsecondary valences is six. Other groups may also be associated with thechromium, but when this occurs, such additional groups are present asions and are outside of the chromium nucleus complex.

In general, the fatty acid chromium complex salts of this invention arefatty acid chromic sulphate complexes and may be formed by reacting ametallic salt of a fatty acid with basic chromic sulphate.

Various fatty acids may be used in the formation of the chromic sulphatecomplex of this invention. Some of them are stearic acid, oleic acid,linoleic acid, cod liver oil fatty acids, decanoic acid, etc. The acidsmay be saturated or unsaturated. The saturation does not have an effecton the complex formation, but does have an effect on the color, thehardness of complex, and after effects such as polymerization, etc.These acids are long chain hydrocarbons compounds containing at least 10carbon atoms and up to and about 25 carbon atoms.

These various fatty acids are reacted with basic metal compounds toproduce the metal salt of the fatty acid. The basic metals are of thealkali metal series.

The basic chromic sulphate, with which the hereinbefore defined metalsalt of the fatty acid is reacted, may be purchased on the commercialmarket, or it may be produced by the reduction of sodium dichromate withsulfur dioxide and also by the reduction of sodium dichromate witheither sucrose or dextrose in the presence of sulfuric acid.

The basicity of the chromic sulphate can range from zero to that degreewhich will leave enough sulphate present in the complex equal to thesulphate displaced by the fatty acid radical to form our complexcompound plus the minimum amount of sulphate necessary to have a complexcompound. Varying basicities may be used so long as they do notinterfere with the reaction of the fatty acid salt and the basic chromicsulphate. The percentage of basicity of the chromic sulphate may bedefined as a measure of the extent to which hydroxyl ions have replacedthe anions of the acid group of the chromic sulphate. For example,chromic sulphate hexahydrate is a chromic salt of the diabasic acid,sulfuric acid, having 0 percent basicity. When the hydroxyl groupreplaces one of the S0 radicals, a basic salt, Cr (OH) (SO is formed andsince one-third of the anionic groups of the chromic sulphate has beenreplaced, this salt is said to be 33.3 percent basic. Similarly, if twoof the S0 radicals are replaced, the compound is said to be 66.6 percentbasic, Cr (OH) SO Thus, chromic hydroxide, Cr(OH) is said to be percentbasic as all of the S0 radicals have been replaced by hydroxyl radicals.As long as there are sufiicient sulphate groups and the compound issoluble the Werner Complex compounds of this invention will form.

While the reaction of the method of this invention will take place undernormal conditions, it has been ascertained that with the addition ofheat and the use of dilute solutions of both the basic chromic sulphateand the fatty acid salts, there is a marked increase in percentage yieldof the fatty acid chromic sulphate complex of this invention.

The complex compounds of this invention are formed in the hydrophobicphase of the reaction mixture and are removed from the reaction mixtureby extraction with mineral spirits, which is a particular cut ofpetroleum consisting primarily of saturated, normal chain hydrocarbons.The complex may then be washed with water to remove any soluble saltsremaining. Also, the water repelling compounds of this invention aresoluble in common aliphatic solvents at room temperature.

The highly purplish color of the compounds of this invention isindicative of the complex formation. Also their solubility at roomtemperature in common aliphatic solvent is another indication. Theconventional sulphate tests were positive in that they disclosed thepresence of sulphates in the complex compound of this invention. It isof interest that the water repelling complex compounds of thisinvention, once affixed to the article to be rendered water repellent,are not soluble in their original solvent, for example mineral spirits;thus their permanent properties.

The fatty acid chromic sulphate compounds of this invention areexcellent water repelling agents. As low as 0.5 gram per 100 mls. ofsolvent applied to articles of paper, leather, cement, cloth, wood, etc.imparts excel lent permanent water repelling properties to the treatedarticle.

The following examples are intended to illustrate the new process of theinstant invention more fully, but are not intended to limit the scope ofthe invention, for it is possible to effect many modifications therein.In the examples, all parts and percents are by weight unless otherwiseindicated.

EXAMPLE 1 To 39 mls. of N/ZNaOH was added grams of stearic acid. Thissolution was heated in a boiling water bath for 45 minutes withintermittent stirring. To this sodium stearate soluton was added 100 ml.of Water and then brought to a boil. To 80 mls. of distilled water wasadded 6 mls. of stock chrome liquor, which was 33 percent basic andcontained 16.7 grams of Cr O per 100 mls. This solution was heated toboiling and then added rapidly with stirring to the boiling sodiumstearate solution. Just prior to the completion of the addition,separation into two layers took place at once with the purplish basicchromic stearate sulphate complex sticking together in a mass and on thesides of the container. The water phase was poured off and 50 mls. ofmineral spirits were added to the precipitate and heated which resultedin the complex dissolving in the hot mineral spirits.

EXAMPLE 2 In a solution of 100 mls. of mineral spirits and 4.38 grams ofthe compound produced in Example 1, having a purplish color, was placeda piece of white cotton twill cloth laundered several times. The twillwas thoroughly soaked and removed from the solution and squeezed. Thecolor of the cloth was purplish. The mineral spirits were allowed toevaporate from the cloth at room temperature. After 5 days a piece ofthe cloth, still purplish in color, was cut off and soaked in mineralspirits. The cloth was removed and no color was found in the mineralspirits and the piece of cloth still retained the purplish color. Thepurplish colored cloth was then placed in new mineral spirits and boiledfor 3 minutes. The cloth was removed, dried and subjected to severalbaths of chloroform. After removal from the chloroform and being allowedto air dry, the cloth was still purplish in color, The cloth would floatwhen placed in water and when water Was poured on it, the water wouldball up and run off leaving the cloth dry.

Thus, after the mineral spirit and chloroform washings, the basicchromic stearate sulphate complex was still fixed to the cloth and gaveit water repellency-a permanent water repelling compound.

The same procedure as above was carried out on filter paper with theexception of a more dilute solution being used so that the filter paperdid not acquire a purplish color. Further, no chloroform washing wasperformed. The filter paper was air dried for 5 days and then soaked inmineral spirits for one hour, removed from this mineral spirits, soakedagain for one hour in fresh mineral spirits and then air dried. Thepaper retained excellent water repelling properties.

EXAMPLE 3 To 35 mls. of N/ZNaOH was added 3 grams of decanoic acid.Enough water was added ot this solution to make 130 mls. This solutionwas heated to boiling with stirring.

To 6 mls. of 33 percent basic chrome sulphate stock solution was added114 mls. of water and then the solution was heated to boiling andrapidly added with stirring to the boiling sodium decanoate. Separationinto two phases took place, the complex forming one phase of a waxy,highly purplish colored compound which adhered to the stirring rod andsides of the container. The second phase was poured off and the basicdecanoate chromic sulphate complex was dissolved in hot mineral spirits.

EXAMPLE 4 The exact procedure of Example 2 was followed except 1 gram ofbasic decanoate chromic sulphate was dissolved in 100 mls. of mineralspirits. White cotton twill cloth and fitler paper were user as inExample 2 and they repelled water as in Example 2.

Pieces of commercial cement blocks were soaked thoroughly in the abovesolution and air dried. These pieces of cement were then heated at 55 C.for 3 hours and then allowed to cool. They repelled water completely.

Thus from the above, cloth, paper and cement, once treated with thewater repelent compound of this invention, acquire permanent waterrepelling characteristics. These compounds, once affixed to thesearticles, cannot be removed by the solvent in which they were originallysoluble.

EXAMPLE 5 To 5 grams of cod liver oil, containing approximately 25percent arachidonic acid, was added 28 mls. of N/ ZNaOH forsaponification. This solution was heated to boiling for 45 minutes withstirring. To this sodium salt of the cod liver oil fatty acid was added100 mls. of water and again brought to a boil.

To mls. of distilled water was added 6 mls. of 33 percent basic chromicsulphate stock solution and then the solution was heated to boiling. Itwas added rapidly with stirring to the above boiling sodium saltsolution of cod liver oil fatty acid. Separation into two phasesoccurred, with a waxy, highly purplish colored compound adhering to thestirring rod and sides of the container. The second phase was poured offand the complex was dissolved in mls. of hot mineral spirits.

EXAMPLE 6 purplish colored soultion, removed and squeezed to remove theexcess. The cloth, now colored highly purplish,

was allowed to dry at room temperature. After 5 days, a piece of thiscloth was immersed in mineral spirits. No purplish color was observed inthe mineral spirits solution and the cloth retained the highly purplishcolor. The piece of cloth was then placed in fresh mineral spirits andheated to a boil and maintained at a boil for 3 minutes. The cloth wasthen subjected to several chloroform washings and then allowed to airdry. No color was observed in the chloroform wash liquid and the clothretained a high purplish color. The cloth was allowed to dry at roomtemperature and then had water poured on it. The water did not soak intothe cloth as it ran off. The thus treated cloth was then placed in acontainer of water and it floated.

Thus, after cleaning the cloth treated with the compound of thisinvention, it was observed that the cloth re tained the water repellingproperties imparted to it by the original treatment of the cloth by thecompound of Example 5. It had acquired permanent water repellingproperties.

Filter paper and commercial cement blocks were treated as above exceptwith a much more dilute solution of the water repelling compound of thisinvention, 1 gram per 100 mls. of mineral spirits. Both the paper andthe block were allowed to air dry. The cement block was then heated at55 C. for about 3 hours, then cooled. When water was poured over theblock, none appeared to penetrate. Upon soaking in water for severalhours and then being removed from the water, there were no wet areas onthe block. It now had excellent permanent water repelling properties.

EXAMPLE 7 A solution of 2.5 grams of stearic acid, 2.5 grams of oleicacid and 120 mls. water was prepared. To this solution was added 36.5mls. of N/ZKOH and then it was heated in a boiling water bath for 30minutes.

A solution of 100 mls. of water and 6 mls. of 33 percent basic chromicsulphate stock solution was prepared and heated to boiling. This boilingsolution was then added with stirring to the above heated solution ofpotassium stearate and potassium oleate.

Two phases formed and in one phase the complex chromic sulphate formedwas waxy and highly purplish in color sticking to the stirring rod andthe sides of the container. The liquid phase was poured off and thecomplex was dissolved in hot mineral spirits.

EXAMPLE 8 The exact procedure of Example 2 was followed and it wasobserved that cloth, paper and cement blocks, when treated with thecompound of Example 7, had acquired permanent water repellency.

Thus, with a treatment of a wide variety of articles by the complexformed by the reaction of alkali metal salt of a fatty acid and a basicchromium sulphate, one can and is able to impart permanent waterrepellency properties to these articles.

It is understood that changes and variations may be made in the presentinvention by one skilled in the art without departing from the spiritand scope thereof as defined in the appended claims.

I claim:

1. A method for producing a permanent 'water repelling compound for manyarticles consisting of reacting a metal salt of a fatty acid, said saltbeing a member selected from the group consisting of the alkali metals,with basic chromic sulphate.

2. The method of claim 1 in which the fatty acids are a member selectedfrom a group consisting of acids containing from 10 carbon atoms up toand around 25 carbon atoms.

3. The method of claim 1 in which the metal salts are a member selectedfrom the group consisting of the alkali metal and the fatty acids are amember selected from a group consisting of acids containing from 10carbon atoms up to and around 25 carbon atoms.

4. The method of claim 1 in which the metal salt is the sodium salt andthe fatty acid is stearic acid.

5. The method of claim 1 in which the metal salt is the sodium salt andthe fatty acid is decanoic acid.

6. The method of claim 1 in which the metal salt is the sodium salt andthe fatty acid is cod liver oil acids.

7. The method of claim 1 in which the metal salt is the potassium saltand the fatty acid is a member selected from the group consisting offatty acids containing from 10 carbon atoms up to and around 25 carbonatoms.

8. The method of claim 7 in which said metal is potassium and said acidis decanoic.

9. A complex compound formed as a reaction product of the mixing ofchromium sulphate and an alkali metal salt of a fatty acid, the carbonchain of said acid containing from 10 to 25 carbon items, said compoundbeing a coordination compound of the Werner type and being furthercharacterized by being generally soluble at room temperature in commonaliphatic :solvents and insoluble in water, said compound also beingcapable of rendering objects with which the compound is treated waterrepellant.

10. The complex compound of claim 9 in which said fatty acid is stearicacid and the alkali metal is sodium.

11. The complex compound of claim 9 in which said fatty acid is decanoicacid.

12. The complex compound of claim 9 in which said fatty acid is codliver oil acids.

13. The complex compound of claim 9 in which said fatty acid is a memberselected from the group consisting of decanoic, stearic, arachidonic andmixtures thereof and the alkali metal is a member selected from thegroup consisting of sodium, potassium and mixtures thereof.

References Cited Iler: Industrial and Engineering Chemistry, vol. 46,No. 4 (1954), pp. 766-769 relied on.

Mellovs Modern Inorganic Chemistry, Revised Ed. by 'Parkes (1961),published by Longmans, New York, pp. 873-875 and 946-947 relied on.

ELBERT L. ROBERTS, Primary Examiner US. Cl. X.R.. 117--l67; 260-18

